JP2008283101A - Method of manufacturing semiconductor device and substrate processing apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing semiconductor devices and a substrate processing apparatus capable of greatly contributing to high nuclear density formation. <P>SOLUTION: The method of manufacturing semiconductor devices includes a step of carrying a wafer 200, on the surface of which an insulating film is formed, into a reaction tube 203, a step of carrying out processing for forming silicon grains on the insulating film formed on the surface of the wafer 200 by introducing at least a silicon-based gas into the reaction tube 203, and a step of carrying the processed wafer out from the reaction tube 203, wherein in the step of carrying out this processing, when the silicon-based gas is solely introduced, the silicon-based gas and a dopant gas are introduced in the reaction tube 203 which is set at a temperature and pressure at which the silicon-based gas does not thermally decompose, so that the flow rate of the dopant gas can be equal to or greater than that of the silicon-based gas. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a semiconductor device manufacturing method and a substrate processing apparatus including a step of forming fine island-like grains (grains) of silicon on a nanoscale and a step of forming fine grain-sized polysilicon. .

  There is a tendency that the tunnel oxide film is made thinner as the flash memory is miniaturized and the operating power is reduced to reduce power consumption. However, while the film thickness is reduced, there is a concern that the reliability of the device is lowered due to dielectric breakdown or stress-induced leakage current. Therefore, unlike a floating gate type or an insulating trap type, a silicon microcrystal memory having an intermediate structure is attracting attention as a memory structure.

  In addition, as the area of the gate electrode occupies a tendency to decrease with higher integration of the DRAM, there is a concern that processing variations of polysilicon crystal grains in the gate electrode may occur as variations in electrical characteristics. For this reason, studies are being made to reduce the variation of each gate electrode by reducing the grain size of polysilicon.

  Development of various processes such as silicon microcrystal memory technology and fine polysilicon formation technology is desired by controlling the initial process of silicon deposition on the insulating film. Since the influence of the surface of the insulating film could not be grasped, it was difficult to form fine grains.

  In addition, it is necessary to optimize the formation conditions of silicon microcrystals to form fine grains. However, since the density of silicon grains is greatly affected by the state of the insulating film surface, fine grains are formed with good reproducibility. It was important to manage the surface condition.

  In the silicon microcrystal memory technology and the fine polysilicon formation technology, the nucleus density must be increased in the grain formation process on the wafer surface. However, in conventional nucleation, it is common to control the nuclear density only by adjusting the process conditions, and this method has a problem that it is difficult to obtain a nuclear density that meets the nanoscale order. Causes and countermeasures were desired.

  Accordingly, an object of the present invention is to provide a method for manufacturing a semiconductor device and a substrate processing apparatus that can solve the above-mentioned problems of the prior art and can greatly contribute to the formation of a high nucleus density.

  The first feature of the present invention is that a substrate having an insulating film formed on a surface thereof is carried into a processing chamber, and at least a silicon-based gas is introduced into the processing chamber, and is formed on the surface of the substrate. A process of forming silicon grains on the insulating film; and a process of unloading the processed substrate from the processing chamber. In the process of performing the process, a silicon-based gas is introduced alone. In such a case, the silicon gas and the dopant gas in the processing chamber set at a temperature and pressure that do not cause thermal decomposition of the silicon gas so that the flow rate of the dopant gas is equal to or higher than the flow rate of the silicon gas. There is a method for manufacturing a semiconductor device to be introduced.

  Preferably, in the step of performing the treatment, thermal decomposition of the silicon-based gas occurs with the action of the dopant gas as a trigger.

  Preferably, in the step of performing the treatment, the temperature in the treatment chamber is 200 to 400 ° C., the pressure in the treatment chamber is 130 to 1330 Pa, the flow rate of the silicon-based gas is 100 to 2000 sccm, and the flow rate of the dopant gas is 100. ˜2000 sccm.

  Preferably, the method further includes a step of cleaning the surface of the insulating film formed on the surface of the substrate before the step of carrying in the substrate.

  Preferably, the method further includes a step of washing the surface of the insulating film formed on the surface of the substrate with a diluted hydrofluoric acid aqueous solution before the step of carrying in the substrate.

  Preferably, in the step of performing the treatment, the dopant gas is introduced before the silicon-based gas is introduced and / or when the silicon-based gas is introduced.

  Preferably, in the step of performing the treatment, island-shaped silicon grains, that is, silicon quantum dots are formed by stopping the growth of silicon grains before the plurality of silicon grains contact each other.

  Preferably, in the step of performing the treatment, the silicon grains are grown so that the plurality of silicon grains are in contact with each other to form a continuous silicon grain, that is, a silicon film.

Preferably, in the step of performing the treatment, SiH ₄ or Si ₂ H ₆ is introduced as a silicon-based gas, and PH ₃ , B ₂ H ₆ , BCl ₃ , or AsH ₃ is introduced as a dopant gas.

  In addition, the second feature of the present invention is that a substrate having an insulating film formed on the surface thereof is carried into the processing chamber, and at least a silicon-based gas is introduced into the processing chamber to form the substrate on the surface. A process of forming silicon grains on the insulating film and a process of unloading the processed substrate from the processing chamber. In the process of performing the process, the silicon-based gas is used alone. When introduced, silicon-based gas and dopant gas are introduced into the processing chamber set to a temperature and pressure that do not cause thermal decomposition of the silicon-based gas, and the silicon-based gas is thermally decomposed using the action of the dopant gas as a trigger. A method of manufacturing a semiconductor device is provided.

  The third feature of the present invention is that a processing chamber for processing a substrate having an insulating film formed on the surface thereof, a silicon-based gas supply system for supplying a silicon-based gas into the processing chamber, and the processing chamber A dopant gas supply system for supplying a dopant gas to the substrate, an exhaust system for exhausting the processing chamber, a heater for heating the substrate in the processing chamber, and a temperature and pressure in the processing chamber were independently introduced with a silicon-based gas. In such a case, the temperature and the pressure are set so that the silicon-based gas is not thermally decomposed, and the silicon-based gas and the dopant gas are introduced into the processing chamber in which the temperature and the pressure are set as described above, and the flow rate of the dopant gas is the silicon-based gas. So that the silicon grain is formed on the insulating film formed on the surface of the substrate. Gas supply system, wherein the dopant gas supply system, there the exhaust system, and a controller for controlling the heater, the substrate processing apparatus having a.

  Preferably, the controller controls the dopant gas supply system so that thermal decomposition of the silicon-based gas occurs with the action of the dopant gas as a trigger.

  Preferably, the controller has a temperature in the processing chamber of 200 to 400 ° C., a pressure in the processing chamber of 130 to 1330 Pa, a flow rate of silicon gas of 100 to 2000 sccm, and a flow rate of dopant gas of 100 to 2000 sccm. Thus, the heater, the exhaust system, the silicon-based gas supply system, and the dopant gas supply system are controlled.

  Preferably, the controller controls the silicon gas supply system and the dopant gas supply system to supply a dopant gas before supplying the silicon gas system and / or when supplying the silicon-based gas. To do.

  Preferably, the controller controls the silicon gas supply system and the dopant gas supply system so that the growth of silicon grains stops before the plurality of silicon grains contact each other.

  Preferably, the controller controls the silicon gas supply system and the dopant gas supply system so that silicon grains grow until a plurality of grains come into contact with each other.

Preferably, the silicon gas supply system supplies SiH ₄ or Si ₂ H ₆ , and the dopant gas supply system supplies PH ₃ , B ₂ H ₆ , BCl ₃ , or AsH ₃ .

  The fourth feature of the present invention is that a processing chamber for processing a substrate having an insulating film formed on the surface, a silicon gas supply system for supplying a silicon-based gas into the processing chamber, and a processing chamber. A dopant gas supply system for supplying a dopant gas, an exhaust system for exhausting the processing chamber, a heater for heating the substrate in the processing chamber, and a temperature and pressure in the processing chamber were introduced independently of a silicon-based gas. In such a case, the temperature and pressure are set so that the silicon-based gas is not thermally decomposed, and the silicon-based gas and the dopant gas are introduced into the processing chamber in which the temperature and pressure are set, and the action of the dopant gas is used as a trigger. A controller that controls to perform a process of forming silicon grains on the insulating film formed on the surface of the substrate so as to cause thermal decomposition of the system gas , In a substrate processing apparatus having a.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method and substrate processing apparatus of a semiconductor device which can form the core which forms the high-density grain (grain) of silicon with sufficient control, and can ensure the stable performance can be provided.

  Conventionally, when forming a silicon microcrystal memory composed of silicon quantum dots, etc., first, silicon-based gas is introduced into the processing chamber containing the substrate to form island-like silicon grains, that is, silicon quantum dots on the substrate in a non-doped manner. Then, after the substrate is taken out from the processing chamber, it is common to dope silicon quantum dots formed by an ion implantation method or the like. However, the present inventor has found that silicon quantum dots can be formed while doping impurities by mixing a dopant gas when forming silicon quantum dots. Further, in the treatment chamber set to a temperature and pressure at which the silicon-based gas is not thermally decomposed when the silicon-based gas flows alone, the silicon-based gas and the dopant gas whose flow rate is equal to or higher than that of the silicon-based gas. It has been found that there is an unprecedented effect that silicon gas can be thermally decomposed by the action of the dopant gas as a trigger to increase the nuclear density of silicon grains.

  The present invention is based on the above findings found by the present inventor. For example, fine silicon for forming a silicon microcrystal memory or a gate electrode made of silicon quantum dots on the surface of a predetermined insulating film of a semiconductor chip. When processing to form grains, when a silicon-based gas is flowed alone, a silicon-based gas and a dopant gas are introduced into a processing chamber set at a temperature and pressure such that the silicon-based gas is not thermally decomposed. The Si nucleus density is increased by introducing the gas at a flow rate equal to or higher than the flow rate of the silicon-based gas.

Embodiments of the present invention will be described below with reference to the drawings.

[Embodiments to which the present invention is applied]
First, an outline of a substrate processing apparatus 10 to which the present invention is applied will be described with reference to FIGS. 1 and 2. In the substrate processing apparatus 10 to which the present invention is applied, a FOUP (front opening unified pod) is used as a carrier for transporting a substrate such as a wafer. In the following description, front, rear, left and right are based on FIG. That is, with respect to the paper surface shown in FIG. 1, the front is below the paper surface, the back is above the paper surface, and the left and right are the left and right of the paper surface.

  As shown in FIGS. 1 and 2, the substrate processing apparatus 10 includes a first transfer chamber 103 configured in a load lock chamber structure capable of withstanding a pressure (negative pressure) less than atmospheric pressure such as a vacuum state. The casing 101 of the first transfer chamber 103 is formed in a box shape having a hexagonal shape in plan view and closed at both upper and lower ends. The first transfer chamber 103 is provided with a first wafer transfer device 112 that simultaneously transfers two wafers 200 under negative pressure. The first wafer transfer device 112 is configured to be moved up and down by the elevator 115 while maintaining the airtightness of the first transfer chamber 103.

  The two side walls located on the front side of the six side walls of the housing 101 are connected to the carry-in spare chamber 122 and the carry-out spare chamber 123 via gate valves 130 and 127, respectively. Each has a load lock chamber structure that can withstand negative pressure. Further, a substrate placing table 140 for loading / unloading chamber is installed in the spare chamber 122, and a substrate placing table 141 for unloading is installed in the spare chamber 123.

  A second transfer chamber 121 used under a substantially atmospheric pressure is connected to the front side of the preliminary chamber 122 and the preliminary chamber 123 via gate valves 128 and 129. In the second transfer chamber 121, a second wafer transfer device 124 for transferring the wafer 200 is installed. The second wafer transfer device 124 is configured to be moved up and down by an elevator 126 installed in the second transfer chamber 121, and is configured to be reciprocated in the left-right direction by a linear actuator 132. .

  As shown in FIG. 1, a notch or orientation flat aligning device 106 is installed on the left side of the second transfer chamber 121. In addition, as shown in FIG. 2, a clean unit 118 that supplies clean air is installed above the second transfer chamber 121.

  As shown in FIGS. 1 and 2, on the front side of the housing 125 of the second transfer chamber 121, a wafer loading / unloading port 134 for loading / unloading the wafer 200 into / from the second transfer chamber 121. A pod opener 108 is installed. An IO stage 105 is installed on the opposite side of the pod opener 108 across the wafer loading / unloading port 134, that is, on the outside of the housing 125. The pod opener 108 includes a closure 142 that can open and close the cap 100 a of the pod 100 and close the wafer loading / unloading port 134, and a drive mechanism 136 that drives the closure 142, and the pod placed on the IO stage 105. By opening and closing the 100 cap 100a, the wafer 200 can be taken in and out of the pod 100. The pod 100 is supplied to and discharged from the IO stage 105 by an in-process transfer device (RGV) (not shown).

  As shown in FIG. 1, two side walls located on the rear side (back side) of the six side walls of the housing 101 are provided with a first processing furnace 202 that performs a desired process on the wafer. The second processing furnace 137 is connected to each other through gate valves 244 and 131 adjacent to each other. Each of the first processing furnace 202 and the second processing furnace 137 is configured by a hot wall type processing furnace. In addition, a first cooling unit 138 and a second cooling unit 139 are connected to the remaining two opposite side walls of the six side walls of the housing 101, respectively. Both the cooling unit 138 and the second cooling unit 139 are configured to cool the processed wafer 200.

  Next, an outline of the first processing furnace 202 of the substrate processing apparatus 10 according to the embodiment of the present invention will be described with reference to FIG. FIG. 3 is a schematic longitudinal sectional view of the first processing furnace 202 of the substrate processing apparatus 10 according to the embodiment of the present invention.

  A reaction tube 203 as a reaction vessel made of quartz, silicon carbide, or alumina has a flat space in the horizontal direction, forms a processing chamber therein, and accommodates a wafer 200 as a substrate. A wafer support 217 as a support for supporting the wafer 200 is provided inside the reaction tube 203, and a gas introduction flange 209 a and a gas exhaust flange 209 b as manifolds are provided at both ends of the reaction tube 203. The first transfer chamber 103 is connected to the introduction flange 209a via a gate valve 244 as a gate valve.

  A first gas introduction line 232a and a second gas introduction line 232b as supply pipes are connected to the gas introduction flange 209a. A first gas source 243a and a second gas source 243b are connected to the first gas introduction line 232a and the second gas introduction line 232b, respectively. In the middle of the first gas introduction line 232a and the second gas introduction line 232b, flow rates for controlling the flow rates of the first gas and the second gas introduced into the reaction tube 203 from the first gas source 243a and the second gas source 243b, respectively. A first mass flow controller 241a and a second mass flow controller 241b as control devices (flow rate control means), and first valves 242a and 240a and second valves 242b and 240b provided on the upstream side and the downstream side are provided, respectively. ing.

A third gas introduction line 232c is connected to the first gas introduction line 232a and the second gas introduction line 232b. A third gas source 243c is connected to the third gas introduction line 232c, and the third gas introduction line 232c is configured to control the flow rate of the third gas introduced into the reaction tube 203 from the third gas source in the middle of the third gas introduction line 232c. A three mass flow controller 241c and a third valve 242c provided on the upstream side thereof are provided. The third gas introduction line 232c branches into two lines downstream of the third mass flow controller 241c, each downstream of the first valve 240a of the first gas introduction line 232a and the second of the second gas introduction line 232b. Connected to the downstream side of the two valves 240b, the third gas can be supplied to each line. In addition, a fourth valve 240c and a fifth valve 240d are provided in each branched line of the third gas introduction line 232c. In the present embodiment, the third gas source 243 contains an inert gas such as N ₂ , Ar, or He as the third gas.

  An exhaust line 231 as an exhaust pipe is connected to the gas exhaust flange 209b. The exhaust line 231 is connected to a vacuum pump 250 as a vacuum exhaust device (exhaust means) for exhausting the inside of the reaction tube 203, and a pressure control unit (for controlling the pressure in the reaction tube 203 (on the way) A pressure controller 248 is provided as a pressure control means).

  An upper heater 207a and a lower heater 207b are provided above and below the reaction tube 203 as heating mechanisms (heating means), respectively, so that the inside of the reaction tube 203 is heated uniformly or with a predetermined temperature gradient. . The upper heater 207a and the lower heater 207b are connected to temperature controllers 247a and 247b as temperature control units (temperature control means) for controlling the respective heater temperatures. Further, a heat insulating material 208 as a heat insulating member is provided so as to cover the upper heater 207a, the lower heater 207b, and the reaction tube 203.

  The temperature in the reaction tube 203, the pressure in the reaction tube 203, and the flow rate of the gas supplied into the reaction tube 203 are set to a predetermined temperature by a temperature controller 247a, 247b, a pressure controller 248, and a mass flow controller 241a, 241b, 241c, respectively. The pressure and flow rate are controlled respectively. The temperature controllers 247a and 247b, the pressure controller 248, and the mass flow controllers 241a, 241b, and 241c are controlled by a main controller 249 as a main control unit (main control means). The main controller 249 is configured to control the opening and closing of the valves 242a, 240a, 242b, 240b, 242c, 240c, and 240d, and also to control the timing of gas supply. Further, the main controller 249 is configured to control the operation of each unit constituting the substrate processing apparatus 10.

  Next, a method of processing a wafer as a substrate as one step of the semiconductor device manufacturing process using the first processing furnace 202 of the substrate processing apparatus 10 described above will be described. In the following description, the operation of each part constituting the substrate processing apparatus 10 is controlled by the main controller 249.

  A thin insulating film such as a silicon oxide film is formed on the wafer 200 as a substrate having semiconductor chips in a step before the processing of this process. Since the performance of the insulating film depends on the electrical characteristics, control and management of the thickness of the thin film is very important. Therefore, conventionally, after the formation of a thin insulating film, cleaning is not performed before performing this process, that is, processing for forming silicon grains (silicon grains).

  On the other hand, in this embodiment, before carrying a wafer having semiconductor chips into the substrate processing apparatus, surface contamination such as natural oxide film or organic contamination is preliminarily treated, for example, by dilute hydrofluoric acid solution (DHF). Then, the substrate is cleaned and removed by using a spin dry drier, etc., and quickly transferred to a spare chamber in the substrate processing apparatus while being clean. The reason why the processing is performed quickly and cleanly is to prevent adverse effects due to the contamination of the atmosphere in the clean room, and it is necessary to manage and control the contamination until the substrate is transferred to the substrate processing apparatus. If there is a lot of contamination on the wafer surface at this point, the bonding density of silicon and the like differs between the state of the insulating film surface and the state of the organic contamination surface, for example. May not be formed, which causes a decrease in the yield of the semiconductor device.

  According to this embodiment, after cleaning and cleaning the surface of the insulating film formed on the substrate surface, the substrate is quickly put into the substrate processing apparatus and processed while being clean. It is possible to avoid depending on the surface state depending on the storage state of the substrate, whereby silicon grains can be stably formed.

  As described above, the unprocessed wafers 200 whose surface cleaning has been completed are transported by the in-process transport apparatus to the substrate processing apparatus for performing the processing process in a state where 25 wafers are accommodated in the pod 100. As shown in FIG. 1 and FIG. 2, the pod 100 that has been transported is delivered and placed on the IO stage 105 from the in-process transport device. The cap 100a of the pod 100 is removed by the pod opener 108, and the wafer loading / unloading port of the pod 100 is opened.

  When the pod 100 is opened by the pod opener 108, the second wafer transfer machine 124 installed in the second transfer chamber 121 picks up the wafer 200 from the pod 100 and loads it into the preliminary chamber 122. Is transferred to the substrate table 140. During the transfer operation, the gate valve 130 on the first transfer chamber 103 side of the preliminary chamber 122 is closed, and the negative pressure in the first transfer chamber 103 is maintained. When the transfer of a predetermined number of, for example, 25 wafers 200 stored in the pod 100 to the substrate table 140 is completed, the gate valve 128 is closed, and the inside of the preliminary chamber 122 is negatively charged by an exhaust device (not shown). Exhausted.

  When the pressure in the preliminary chamber 122 reaches a preset pressure value, the gate valve 130 is opened, and the preliminary chamber 122 communicates with the first transfer chamber 103. Subsequently, the first wafer transfer device 112 in the first transfer chamber 103 picks up the wafers 200 from the substrate placing table 140 two by two and carries them into the first transfer chamber 103. After the gate valve 130 is closed, the first transfer chamber 103 and the first processing furnace 202 are communicated with each other. That is, the gate valve 244 is opened while the temperature in the reaction tube 203 is maintained at the processing temperature by the heaters 207a and 207b, and the wafer 200 is loaded into the reaction tube 203 by the first wafer transfer device 112. Placed on the wafer support 217. In this example, two wafers 200 are placed on the wafer support 217, and the two wafers 200 are processed simultaneously. Note that two wafers 200 are simultaneously transferred into the reaction tube 203 in order to equalize the thermal history of the two wafers 200 to be processed simultaneously. At the same time that the wafer 200 is loaded into the reaction tube 203, the temperature rise (preheating) to the processing temperature of the wafer 200 is started. Note that it is possible to place only one wafer 200 on the wafer support base 217, and one wafer 200 may be processed at a time. In that case, it is preferable to place a dummy wafer on a support portion of the wafer support base 217 that does not support the wafer 200.

  After the first wafer transfer device 112 is moved backward and the gate valve 244 is closed, the pressure in the reaction tube 203 is controlled by the pressure controller 248 (pressure stabilization) so as to become the processing pressure. Are controlled by temperature controllers 247a and 247b so that the wafer temperature becomes the processing temperature (temperature stabilization). When the pressure in the reaction tube 203 is stabilized and the temperature of the wafer 200 is stabilized, the first gas introduction line 232a and the second gas are introduced into the reaction tube 203 from the third gas source 243c through the third gas introduction line 232c. By introducing an inert gas from at least one of the two gas introduction lines 232b, the reaction tube 203 is filled with an inert gas atmosphere.

  After the pressure in the reaction tube 203 is stabilized at the processing pressure and the temperature of the wafer 200 is stabilized at the processing temperature, the processing gas is introduced into the reaction tube 203, whereby the wafer 200 is processed. That is, silicon grains are formed on the insulating film formed on the wafer 200.

At this time, silicon particles are formed by introducing a silicon-based gas such as SiH ₄ or Si ₂ H ₆ into the reaction tube 203. Conventionally, the density of silicon particles is 10 ¹⁰ pieces / cm ² to 10 ¹¹ pieces / cm ² level. As the gate electrode length becomes smaller as the device becomes more highly integrated, it is desired to form silicon grains with a high density of small grains to alleviate the variation. However, with the conventional method, it has been difficult to form target silicon grains of 10 ¹² / cm ² level.

Accordingly, in the process of the present invention, silicon is formed by performing treatment under conditions that form many nucleation sites of silicon grains using a dopant gas such as PH ₃ , B ₂ H ₆ , BCl ₃ , AsH _3. The density of grain formation was increased.

That is, in the present embodiment, the first gas source 243a contains a silicon-based gas such as SiH ₄ or Si ₂ H ₆ as the first gas, and the second gas source 243b contains PH ₃ as the second gas, A dopant gas such as B ₂ H ₆ , BCl ₃ , AsH ₃ is accommodated, the pressure in the reaction tube 203 is stabilized at the processing pressure, and the temperature of the wafer 200 is stabilized at the processing temperature. The silicon gas as the first gas and the dopant gas as the second gas are introduced from the first gas source 243a and the second gas source 243b through the first gas introduction line 232a and the second gas introduction line 232b at the timing described later. As a result, silicon particles are formed on the insulating film formed on the wafer 200.

  Specifically, (1) the dopant gas is first introduced into the reaction tube 203 and the introduction of the dopant gas is stopped, and then the silicon-based gas is introduced to form silicon grains, or (2) Introduce dopant gas and silicon-based gas simultaneously to form silicon grains, or (3) Introduce dopant gas in advance and introduce silicon-based gas while maintaining introduction of dopant gas to form silicon grains I tried to do it.

  During the process of forming silicon grains, the temperature and pressure in the processing chamber are set to a temperature and pressure that do not cause thermal decomposition of the silicon-based gas when the silicon-based gas is flowed alone, and the dopant gas flow rate is set to silicon. It was set to be equal to or more than the flow rate of gas system gas.

That is, (1) before the process of forming silicon grains, (2) during the process of forming silicon grains, or (3) before and during the process of forming silicon grains, the dopant gas is introduced into the process chamber. When the silicon gas is flowed alone, the temperature and pressure in the processing chamber are set to such a temperature and pressure that the silicon gas is not thermally decomposed. It was set to be equal to or more than the flow rate. In this way, 10 ¹² / cm ² level silicon grains can be formed as will be described later.

In addition, when processing a wafer in the processing furnace of this embodiment, that is, as processing conditions when forming silicon grains on the insulating film formed on the wafer surface, for example, a processing temperature of 200 to 400 ° C., a processing pressure Examples include 130 to 1330 Pa, a silicon-based gas (SiH ₄ ) flow rate of 100 to 2000 sccm, and a dopant gas (B ₂ H ₆ ) flow rate of 100 to 2000 sccm, and each processing condition is kept constant at a predetermined value within each range. Thus, silicon grains can be formed while increasing the number of nucleation sites of silicon grains.

  Next, steps from nucleation to continuous film formation will be described with reference to FIG. As shown in FIG. 4A, when a silicon-based gas is supplied, nuclei are formed on the insulating film on the substrate surface, and then, as shown in FIG. 4B, crystals grow around the nuclei. This grown crystal is called a grain. As shown in FIG. 4C, when the grains further grow, the grains come into contact with each other. As shown in FIG. 4D, when there is no gap between the grains, a polysilicon film is formed as a continuous film. It should be noted that island-like grains, that is, silicon quantum dots can be formed by stopping the growth in a state where the grains before the grains are in contact with each other are independent.

  In the present invention, the process of forming the grains while flowing the dopant gas before and / or during the process of forming the grains, that is, before the supply of the silicon-based gas and / or during the supply of the silicon-based gas, is performed as described above. The nucleation density is increased by performing processing at a processing temperature, processing pressure and gas flow rate that increase the number of nucleation sites. As a result, the density of silicon grains can be increased when forming silicon quantum dots, and the grain size of the polysilicon film can be made fine when forming a polysilicon film.

  When the processing of the wafer 200 is completed, in order to remove the residual gas in the reaction tube 203, the gas introduction lines 232a and 232b are provided in the reaction tube 203 from the third gas source 243c through the third gas introduction line 232c. While the inert gas as the third gas is introduced from at least one of them, the gas is exhausted from the exhaust line 231 and the reaction tube 203 is purged.

  After purging in the reaction tube 203, the pressure in the reaction tube 203 is adjusted by the pressure controller 248 so as to become the wafer transfer pressure. After the pressure in the reaction tube 203 becomes the transfer pressure, the processed wafer 200 is unloaded from the reaction tube 203 to the first transfer chamber 103 by the first wafer transfer device 112. That is, when the processing for the wafer 200 is completed in the first processing furnace 202 and the purge is completed, the gate valve 244 is opened, and the two processed wafers 200 are first processed by the first wafer transfer device 112. It is transferred to the transfer chamber 103. After unloading, the gate valve 244 is closed.

  The first wafer transfer device 112 transports the two wafers 200 unloaded from the first processing furnace 202 to the first cooling unit 138, and the two processed wafers 200 are cooled.

  When the processed wafer 200 is transferred to the first cooling unit 138, the first wafer transfer device 112 simultaneously uses two wafers 200 prepared in advance on the substrate mounting table 140 in the preliminary chamber 122 in the same manner as described above. The two wafers 200 are simultaneously subjected to desired processing in the first processing furnace 202 after being picked up and transferred to the first processing furnace 202.

  When a preset cooling time has elapsed in the first cooling unit 138, the two cooled wafers 200 are unloaded from the first cooling unit 138 to the first transfer chamber 103 by the first wafer transfer device 112. Is done.

  After the two cooled wafers 200 are carried out from the first cooling unit 138 to the first transfer chamber 103, the gate valve 127 is opened. The first wafer transfer device 112 transports the two wafers 200 unloaded from the first cooling unit 138 to the preliminary chamber 123 and transfers them to the substrate table 141, and then the preliminary chamber 123 is moved by the gate valve 127. Closed.

  By repeating the above operation, a predetermined number of, for example, 25 wafers 200 carried into the preliminary chamber 122 are sequentially processed two by two.

  When the processing for all the wafers 200 loaded into the spare chamber 122 is completed, all the processed wafers 200 are stored in the spare chamber 123, and the spare chamber 123 is closed by the gate valve 127, the inside of the spare chamber 123 is not stored. The pressure is returned to approximately atmospheric pressure by the active gas. When the inside of the preliminary chamber 123 is returned to approximately atmospheric pressure, the gate valve 129 is opened, and the cap 100 a of the empty pod 100 placed on the IO stage 105 is opened by the pod opener 108. Subsequently, the second wafer transfer device 124 in the second transfer chamber 121 picks up the wafer 200 from the substrate table 141 and carries it out to the second transfer chamber 121, and the wafer transfer into the second transfer chamber 121. The pod 100 is stored through the outlet 134. When the storage of the 25 processed wafers 200 into the pod 100 is completed, the cap 100 a of the pod 100 is closed by the pod opener 108. The closed pod 100 is transferred from the top of the IO stage 105 to the next process by the in-process transfer apparatus.

  The above operation has been described by taking the case where the first processing furnace 202 and the first cooling unit 138 are used as an example, but the case where the second processing furnace 137 and the second cooling unit 139 are used is also described. Similar operations are performed. In the above-described substrate processing apparatus 10, the spare chamber 122 is used for carrying in and the spare chamber 123 is used for carrying out. However, the spare chamber 123 may be used for carrying in, and the spare chamber 122 may be used for carrying out.

  Moreover, the 1st processing furnace 202 and the 2nd processing furnace 137 may perform the same process, respectively, and may perform another process. In the case where different processing is performed in the first processing furnace 202 and the second processing furnace 137, for example, processing in the wafer 200 is performed in the first processing furnace 202, for example, cleaning processing of an insulating film formed on the substrate surface is performed. Subsequently, another process, for example, a silicon grain formation process in the present embodiment may be performed in the second processing furnace 137. In addition, when predetermined processing is performed on the wafer 200 in the first processing furnace 202 and then another processing is performed in the second processing furnace 137, the first processing unit 138 passes through the first cooling unit 138 or the second cooling unit 139. You may make it do.

  Next, Example 1 will be described with reference to FIGS.

[Example 1]
FIG. 5 shows a case where a wafer is processed using the substrate processing apparatus 10 described above, and the wafer surface (insulating film surface) is cleaned before the wafer is processed, and the wafer surface is cleaned before the wafer is processed. The case where the process is not performed indicates how the film thickness of the silicon film formed on the wafer surface tends to increase as the processing time elapses. In the figure, the horizontal axis indicates the processing time (minute), that is, the supply time of the silicon-based gas, and the vertical axis indicates the film thickness (nm) of the silicon film formed on the insulating film on the wafer surface. Further, “without pre-cleaning” indicates that the wafer surface is not cleaned before the wafer is processed, and “pre-cleaning” indicates that the wafer surface is cleaned before the wafer is processed. In either case, the processing conditions for processing the wafer were the same. Specifically, in the wafer processing, the processing temperature is maintained at a predetermined value within a range of 200 to 800 ° C., a processing pressure of 13 to 1330 Pa, and a silicon-based gas (SiH ₄ ) flow rate of 10 to 2000 sccm. went. In Example 1, the treatment was performed using only the silicon-based gas, and no dopant gas was used. Monosilane (SiH ₄ ) was used as the silicon-based gas.

  In the case of normal direct processing without performing the cleaning processing, as shown in “No pre-cleaning” in FIG. 5, it took 8 minutes or more to show the tendency to increase the thickness of the silicon film. During this 8 minutes, reactions such as decomposition, surface adsorption, migration, and dissociation of the silicon-based gas have repeatedly occurred on the wafer surface, and the bond density for adsorbing the silicon-based gas on the wafer surface can be increased by not performing pre-cleaning. It is presumed that the film formation started 8 minutes later, including the amount that the adsorption probability decreased due to a decrease in contaminants. The fact that the adsorption probability is reduced means that there is a factor that decreases the density of silicon grains on the wafer surface. Usually, grains grow in a three-dimensional direction from a low density of silicon grains, and the film thickness is increased. It is estimated that it will increase. Such a surface state indicates that the formation of silicon grains cannot be controlled by the supply conditions of the silicon-based gas.

  On the other hand, when the cleaning process is performed, as shown in “with pre-cleaning” in FIG. 5, it takes about 5 minutes until the silicon film has a tendency to increase in film thickness. The result was shorter by about 3 minutes. This difference of 3 minutes is considered to depend on the number of bonds on the wafer surface. As mentioned above, reactions such as decomposition, surface adsorption, migration, and dissociation of silicon gas repeatedly occur on the wafer surface, and the bond density for silicon gas adsorption on the wafer surface is pre-cleaned by pre-cleaning. Unlike the case where no cleaning is performed, that is, it is larger than when no pre-cleaning is performed, and is determined by the film state on the wafer surface. As a result, the adsorption probability is also improved.

  Here, with reference to FIG. 6, the reaction mode with and without the pre-cleaning will be described. FIG. 6 is an image diagram of the reaction mode when the pre-cleaning is performed and when it is not performed. The reaction form changes depending on the clean state of the surface of the insulating film formed on the silicon substrate. That is, when pre-cleaning is not performed before the step of performing the process of forming silicon grains, as shown in FIG. 6A, bonding of the insulating film when the silicon-based gas reacts on the surface If another contaminating molecule (CxHy, O, etc.) is bound to the hand, silicon particles are difficult to form. That is, the formation of silicon grains depends on the surface state, and the formation of silicon grains cannot be controlled by the supply conditions of the silicon-based gas. On the other hand, when pre-cleaning is performed, as shown in FIG. 6B, the surface of the insulating film is in a clean surface state free of contaminants, and the bonding hands of the insulating film have a low temperature such as hydrogen (H). If atoms that are easy to detach are bonded, silicon grains are easily formed. That is, the formation of silicon grains can be controlled by the supply conditions of the silicon-based gas.

  Accordingly, in the present invention, as described in the above embodiment, the silicon surface is cleaned by pretreatment (pre-cleaning) before performing the treatment for forming silicon grains in the treatment chamber (reaction vessel). It is possible to form nuclei that form fine grains with good control. Thereby, stable performance of the semiconductor device can be ensured.

  Next, Example 2 will be described with reference to FIGS.

[Example 2]
FIG. 7 is an electron microscope image showing the effect of controlling the silicon grain density according to the presence or absence of the supply of the dopant gas and the difference in the supply timing found by experiments using the processing furnace of the substrate processing apparatus 10 described above. It is. FIG. 8 shows the supply timing of the silicon-based gas and dopant gas. In this example, monosilane (SiH ₄ ) was used as the silicon-based gas, and diborane (B ₂ H ₆ ) was used as the dopant gas. The wafer is processed at a processing temperature of 200 to 800 ° C., a processing pressure of 13 to 1330 Pa, a silicon-based gas (SiH ₄ ) flow rate of 10 to 2000 sccm, and a dopant gas (B ₂ H ₆ ) flow rate of 10 to 2000 sccm. The test was carried out while maintaining a constant value. In this example, the wafer was processed after the pre-cleaning shown in the above embodiment.

  The three images A, B, and C are obtained by processing the wafer by sequences A, B, and C as shown in FIG. That is, the sequence A is prior to the process of forming the silicon grains and when only the silicon-based gas is flown without flowing the dopant gas during the process, the sequence B is the flow of the dopant gas only before the process, and the sequence C is prior to the process. And when the dopant gas is continuously flowed during the process. Thus, it experimented by controlling so that the timing which flows dopant gas might be varied.

In the case of the conventional treatment that does not flow the dopant gas as in A shown in FIG. 7, the density of silicon grains is 10 ¹¹ particles / cm ² level, but the dopant gas is flowed as in B and C shown in FIG. This increases the density of silicon grains.

According to this embodiment, as shown in FIG. 7C, silicon particles are formed at a high density of 10 ¹² particles / cm ^{2 in the} case of flowing a dopant gas before and during the process of forming silicon grains. 7A, it was found that the density of the silicon grains was increased by about 10 times compared to the case before the process of forming the silicon grains and when the dopant gas was not passed during the process.

  This means that by flowing the dopant gas, the bond density and bonding state for adsorbing the silicon-based gas on the wafer surface are different from those when the dopant gas is not flowed.

  This 10-fold density difference is considered to depend on the state of the bond on the wafer surface. As described above, when silicon-based gas is introduced to form silicon grains, reactions such as surface adsorption, migration, decomposition, and dissociation of the silicon-based gas are repeatedly generated on the wafer surface, and the bonds on the wafer surface Adsorption of hydrogen separated from dopant atoms and dopant gas increases the bond density for silicon-based gas adsorption compared to when no dopant gas is flowed, or absorbs hydrogen for easy decomposition of silicon-based gas It is presumed that the silicon gas density was improved by increasing the decomposition probability of the silicon-based gas.

  Here, with reference to FIG. 9, a description will be given of a reaction mode between when the dopant gas is supplied and when it is not supplied before and / or during the process of forming the silicon grains. FIG. 9 is an image diagram of a reaction mode between FIG. 9B when the dopant gas is supplied before and / or during the process of forming the silicon grains, and FIG. 9A when the dopant gas is not supplied.

When a dopant gas is flowed before, during, or before and during the process of forming silicon grains on the surface of the insulating film formed on the silicon substrate, the dopant gas is insulated at the surface of the insulating film. Bonds with the bond on the membrane surface. FIG. 9B shows a state in which the dopant gas containing boron (B) is decomposed and the dopant atoms, that is, boron atoms are bonded to the bonds on the surface of the insulating film. Thereby, the formation of silicon grains depends on the adsorption state of the dopant gas and dopant atoms on the insulating film surface.

  The silicon particles are formed by the silicon-based gas adsorbed on the surface of the insulating film, and the decomposed silicon atoms (Si) moving on the surface of the insulating film and fixing at a place where a plurality of silicon atoms gathered. Therefore, when the dopant gas is adsorbed on the surface of the insulating film, as shown in the lower diagram of FIG. 9B, the dopant gas restricts the movement range of the silicon atoms, and as a result, minute silicon particles Can be formed with high density. That is, the formation of silicon grains can be controlled by the supply of the dopant gas and the supply conditions of the dopant gas.

  On the other hand, when the dopant gas is not flowed before and / or during the process of forming the silicon grains, as shown in FIG. 9A, the movement range of the silicon atoms is not limited. Compared to the above, it becomes difficult to form fine silicon grains at high density.

  As described above, according to the present invention, in the case where the formation of high-density silicon grains is intended, the dopant is introduced before or during the process of introducing silicon-based gas into the processing chamber to form silicon grains, or before and during the process. Since the gas is allowed to flow, nuclei that form high-density silicon grains can be formed with good control, whereby stable performance of the semiconductor device can be ensured.

  Next, Example 3 will be described with reference to FIGS.

Example 3
FIG. 10 is an electrophotographic microscopic image showing the effect of controlling the silicon grain density by the difference in processing temperature, processing pressure, and gas flow rate found by experiments using the processing furnace of the substrate processing apparatus 10 described above. is there. FIG. 11 shows the supply timing of the silicon-based gas and the dopant gas. In this example, monosilane (SiH ₄ ) was used as the silicon-based gas, and diborane (B ₂ H ₆ ) was used as the dopant gas. In this example, the wafer was processed after the pre-cleaning shown in the above embodiment.

  The two images D and E are both obtained by processing the wafer according to a sequence as shown in FIG. However, the processing conditions are set differently. The image D is an image obtained when processing is performed under processing condition 1 described later, and the image E is an image obtained when processing is performed under processing condition 2 described later.

The processing condition 1 is that the temperature and pressure in the processing chamber are set to a temperature and pressure at which the silicon-based gas is thermally decomposed when the silicon-based gas is flowed alone, and the processing pressure is set low to suppress the growth of silicon grains. The total flow rate including the dopant gas flow rate and the silicon-based gas flow rate is set to a relatively small amount. Specifically, processing conditions 1 include a processing temperature of 500 to 700 ° C., a processing pressure of 10 to 100 Pa, a silicon-based gas (SiH ₄ ) flow rate of 10 to 100 sccm, and a dopant gas (B ₂ H ₆ ) flow rate of 10 to 50 sccm. Then, the wafer was processed by keeping the respective processing conditions constant at predetermined values within the respective ranges.

On the other hand, the processing condition 2 is to set the temperature and pressure in the processing chamber to such a temperature and pressure that the silicon-based gas is not thermally decomposed when the silicon-based gas is flowed alone, so as to ensure the growth rate of silicon grains. In order to promote the decomposition reaction of the silicon-based gas, the flow rate of the dopant gas is set equal to or higher than the flow rate of the silicon-based gas, and the total gas flow rate is set. Specifically, processing conditions 2 include a processing temperature of 200 to 400 ° C., a processing pressure of 130 to 1330 Pa, a silicon-based gas (SiH ₄ ) flow rate of 100 to 2000 sccm, and a dopant gas (B ₂ H ₆ ) flow rate of 100 to 2000 sccm. Then, the wafer was processed by keeping the respective processing conditions constant at predetermined values within the respective ranges. As described above, the experiment was performed by controlling the processing temperature, the processing pressure, and the gas flow rate to be different.

As a result of the experiment, when the silicon gas is flowed alone, the temperature and pressure at which the silicon gas is thermally decomposed are set, and when processing is performed under the condition 1 that is relatively high temperature, low pressure and small flow rate, silicon The density of the grains was 7 × 10 ¹¹ particles / cm ² . In addition, when silicon gas is flowed alone, the temperature and pressure are set so that silicon is not thermally decomposed, and when processing is performed under conditions 2 that are relatively low temperature, high pressure, and large flow rate, The density of was 1.3 × 10 ¹² pieces / cm ² . Thus, under condition 2, the density of silicon grains is increased approximately twice as much as in condition 1.

  The reason why the density of silicon grains formed under condition 2 is higher than that of condition 1 is that the reaction such as surface adsorption / migration / decomposition / dissociation of the silicon-based gas that occurs on the wafer surface varies depending on the condition. It is done. That is, the surface adsorption probability is increased by forming silicon grains at a high pressure as in this embodiment. In addition, by forming silicon grains at a low temperature, migration is suppressed and bonding between silicon grains is less likely to occur. Furthermore, by setting the flow rate of the dopant gas to be equal to or higher than the flow rate of the silicon-based gas and increasing the total flow rate of the gas, the decomposition of the silicon-based gas is promoted, and at a temperature at which the silicon-based gas alone is not thermally decomposed. In addition, silicon grains can be formed. For these reasons, it is considered that the silicon grain density is improved under the condition 2 as compared with the condition 1.

In addition to improving the silicon particle density as described above, the gas flow rate is increased, and the silicon density distribution and silicon particle size distribution in the wafer surface are made uniform. Is mentioned. The silicon particle size can be controlled by controlling the time during which the silicon-based gas flows.

Here, referring to FIG. 12, the reaction mode between the case where the silicon grain forming process is performed at a low pressure and the case where the silicon grain forming process is performed at a high pressure, and the case where the silicon grain forming process is performed at a high temperature with reference to FIG. The reaction mode when the process is performed at a low temperature will be described with reference to FIG. 14 when the process for forming silicon grains is performed at a low flow rate and when the process is performed at a high flow rate. Description will be made using SiH ₄ as an example of a silicon-based gas and B ₂ H ₆ as an example of a dopant gas.

FIG. 12 is an image diagram of a reaction mode when the process for forming silicon grains is performed at a low pressure (FIG. 12A) and when the process is performed at a high pressure (FIG. 12B). In FIG. 12, when performing the process of forming silicon grains on the surface of the insulating film formed on the silicon substrate, surface adsorption of silicon-based gas, dissociation, decomposition into silicon atoms (Si), and surface movement of silicon atoms are performed on the surface of the insulating film. Reaction such as (migration) has occurred. Compared with the case where the silicon grain formation process is performed at a high pressure (FIG. 12B) and the case where the process is performed at a low pressure (FIG. 12A), a silicon-based gas, a dopant gas, that is, SiH ₄ molecules, B ₂ H _Since many ₆ molecules exist in the space, the surface adsorption amount of the silicon-based gas and the dopant gas increases. Many silicon-based gases adsorbed on the surface are decomposed into silicon atoms (Si), and the dopant gas is decomposed into dopant atoms, that is, boron atoms (B), and combined with bonds on the surface of the insulating film.

  Silicon grains are formed by the silicon-based gas adsorbed on the surface of the insulating film, and the decomposed silicon atoms (Si) moving on the surface of the insulating film and fixing at a place where a plurality of silicon atoms gathered. Therefore, when a large number of dopant atoms are adsorbed on the surface of the insulating film, as shown in the lower diagram of FIG. Can be formed with high density. That is, the formation of silicon grains can be controlled by the supply of the dopant gas and the supply conditions of the dopant gas.

In addition, since the higher the pressure, the more silicon-based gas and dopant gas, that is, SiH ₄ molecules and B ₂ H ₆ molecules exist in the space, the movement of silicon atoms adsorbed on the insulating film surface is transferred to the silicon-based gas and dopant gas. Blocked and restricted. As a result, the higher the processing pressure is, the finer the silicon grains can be formed. That is, the formation of silicon grains can be controlled under the pressure conditions when performing the process of forming silicon grains.

  FIG. 13 is an image diagram of a reaction mode when the process for forming silicon grains is performed at a high temperature (FIG. 13A) and when the process is performed at a low temperature (FIG. 13B). In FIG. 13, when a process for forming silicon grains on the surface of the insulating film formed on the silicon substrate is performed, surface adsorption of silicon-based gas, dissociation, decomposition into silicon atoms (Si), and surface movement of silicon atoms are performed on the surface of the insulating film. Such a reaction has occurred. Compared with the case where the process for forming silicon grains is performed at a low temperature (FIG. 13B) and the case where the process is performed at a high temperature (FIG. 13A), the silicon atoms adsorbed on the surface of the insulating film have lower energy. The surface movement of is restricted, and bonding between atoms is difficult to occur. As a result, minute silicon grains can be formed with high density. That is, the formation of silicon grains can be controlled under the temperature conditions when performing the process of forming silicon grains.

  When the process for forming silicon grains is performed at a high temperature as shown in the lower diagram of FIG. 13A, the energy of silicon atoms adsorbed on the surface of the insulating film is high and the silicon atoms move to each other. It becomes easy to bond, and it becomes difficult to increase the density of silicon grains. In addition, when the process for forming silicon grains is performed at a high temperature, it is difficult to control the grain size because the growth rate of silicon grains is high.

FIG. 14 is an image diagram of a reaction mode when the process of forming silicon grains is performed with a small flow rate gas (FIG. 14A) and when the process is performed with a large flow rate (FIG. 14B). In the process of forming silicon grains, when the flow rate of the dopant gas is equal to or higher than the flow rate of the silicon-based gas and the total gas flow rate is a large flow rate (FIG. 14B), the flow rate is small (FIG. 14B). 14 (a)), the flow rate of the silicon-based gas and the dopant gas on the surface of the insulating film formed on the silicon substrate is increased, so that the difference in distribution of silicon grains hardly occurs and the distribution can be made uniform ( FIG. 14 (b)). On the other hand, when the treatment is performed at a small flow rate, the distribution of silicon grains becomes non-uniform because the gas flow rate is low (FIG. 14 (a)). Since the decomposition of the silicon-based gas becomes remarkable, the formation of silicon grains can be performed even at a temperature at which the silicon-based gas alone is not thermally decomposed. That is, the dopant gas also serves as a trigger for silicon-based gas decomposition. By increasing the flow rate, silicon-based gas and dopant gas, that is, SiH ₄ molecules and B ₂ H ₆ molecules are present in a large amount in the space, and a reaction similar to the increase in pressure described with reference to FIG. 12 occurs. Become.

  In this way, the process of forming silicon grains is performed at a high pressure and low temperature that do not cause thermal decomposition of the silicon-based gas when the silicon-based gas is flowed alone, and the dopant gas flow rate is equivalent to the silicon-based gas flow rate. Alternatively, when the flow rate is increased and the flow rate is increased, silicon grains can be formed at a high density, and the silicon grain size can be easily controlled by changing the flow time of the silicon-based gas and the dopant gas over the substrate. Control becomes possible.

  As described above, in this embodiment, when the purpose is to form high-density silicon grains, the temperature and pressure in the processing chamber are such that the silicon-based gas is not thermally decomposed when the silicon-based gas flows alone. In order to secure the growth rate of silicon grains, the pressure in the processing chamber is set high, and the flow rate of the dopant gas is equivalent to the flow rate of the silicon gas in order to promote the decomposition reaction of the silicon gas. Or more, it is possible to satisfactorily form nuclei that form high-density grains of silicon. Therefore, according to this embodiment, it is possible to provide a method of manufacturing a semiconductor device that can ensure stable performance of the semiconductor device.

Here, the flow rate of the dopant gas is equal to the flow rate of the silicon-based gas. For example, the flow rate of the dopant gas is 390 sccm and the flow rate of the silicon-based gas is 400 sccm. Including the case of slightly less. Even when B ₂ H ₆ is used as the dopant gas, SiH ₄ is used as the silicon-based gas, and the flow rate of B ₂ H ₆ is set to 390 sccm with respect to the flow rate of SiH ₄ of 400 sccm, the flow rate of SiH ₄ , B ₂ It was confirmed by experiments that the same effect as that obtained when both the flow rates of H ₆ were 400 sccm was obtained.

  Next, as an example of a manufacturing method of a semiconductor device (device), when manufacturing a flash memory, an example in which the substrate processing apparatus and the substrate processing method of the present invention are applied, that is, the flash memory floating gate is formed of silicon quantum dots. An example of applying the substrate processing apparatus and the substrate processing method of the present invention when configuring will be described. FIG. 15 is a cross-sectional view showing a part of a flash memory including a floating gate composed of silicon quantum dots.

First, a tunnel oxide film 304 made of an insulator such as a silicon oxide film (SiO ₂ film) is formed on the surface of the wafer 200. The tunnel oxide film 304 is formed by, for example, a thermal oxidation method such as dry oxidation or wet oxidation.

  Subsequently, a floating gate electrode 305 composed of a plurality of island-shaped grains, that is, silicon quantum dots 305a is formed on the tunnel oxide film 304 by applying the substrate processing apparatus and the substrate processing method of the present invention. The silicon quantum dots 305a are formed in, for example, a hemisphere or a sphere.

Subsequently, for example, an insulator having a laminated structure of a silicon oxide film (SiO ₂ film) / silicon nitride film (Si ₃ N ₄ film) / silicon oxide film (SiO ₂ film) so as to cover the floating gate electrode 305, etc. An insulating layer 306 made of is formed. The SiO ₂ film constituting the insulating layer 306 is formed by, for example, a CVD method using SiH ₂ Cl ₂ gas and N ₂ O gas, and the Si ₃ N ₄ film is formed by, for example, SiH ₂ Cl ₂ gas and NH ₃ gas Is formed by a CVD method. Thereafter, a control gate electrode 307 made of, for example, a polysilicon film (Poly-Si film) to which phosphorus (P) is added is formed on the insulating layer 306. The control gate electrode 307 is formed by, for example, a CVD method using SiH ₄ gas and PH ₃ gas. As a result, the control gate electrode 307 is formed on the floating gate electrode 305.

  Finally, a source 301 and a drain 302 which are impurity regions to which an n-type impurity is added are formed on the main surface of the wafer 200 by an ion implantation method or the like. A channel region 303 is formed between the source 301 and the drain 302. The flash memory shown in FIG. 15 is manufactured by the above flow.

  Next, as another example of a method for manufacturing a semiconductor device (device), when manufacturing a DRAM, an example in which the substrate processing apparatus and the substrate processing method of the present invention are applied, that is, a part of the gate electrode of the DRAM is finely formed. An example in which the substrate processing apparatus and the substrate processing method of the present invention are applied when forming a polysilicon film having a different grain size will be described. FIG. 16 is a cross-sectional view showing a part of a DRAM including a gate electrode composed of a polysilicon film having a fine grain size and a metal film.

First, a gate oxide film 404 made of an insulator such as a silicon oxide film (SiO ₂ ) or a silicon oxynitride film (SiON) is formed on the surface of the silicon wafer 200. The gate oxide film 404 is formed by a thermal oxidation method such as dry oxidation or wet oxidation, for example.

Subsequently, a polysilicon film 405 composed of fine grains 405a is formed on the gate oxide film 404 by applying the substrate processing apparatus and the substrate processing method of the present invention. Subsequently, a metal film 406 such as tungsten (W) is formed on the polysilicon film 405. The metal film 406 is formed by, for example, an ALD method or a CVD method. As a result, a gate electrode 407 composed of the polysilicon film 405 having a fine grain size and the metal film 406 is formed.
Subsequently, an insulating layer 408 made of, for example, a silicon nitride film (Si ₃ N ₄ film) or the like is formed so as to cover the gate electrode 407. The Si ₃ N ₄ film constituting the insulating layer 408 is formed by, for example, a CVD method using SiH ₂ Cl ₂ gas and NH ₃ gas.

  Finally, a source 401 and a drain 402 which are impurity regions to which an n-type impurity is added are formed on the main surface of the silicon wafer 200 by an ion implantation method or the like. A channel region 403 is formed between the source 401 and the drain 402. With the above flow, the DRAM gate structure shown in FIG. 16 is manufactured.

  The present invention can be applied to a method for manufacturing a semiconductor device such as a flash memory or a DRAM and a substrate processing apparatus.

1 is a plan view of a substrate processing apparatus according to an embodiment to which the present invention is applied. It is sectional drawing of the substrate processing apparatus shown in FIG. It is a schematic sectional drawing of the processing furnace of the substrate processing apparatus which concerns on embodiment of this invention. It is a schematic diagram explaining the formation process of a silicon quantum dot and a polysilicon. It is a graph which shows the relationship between the film-forming time and film thickness increase in Example 1 of this invention. The reaction image in Example 1 of this invention is shown, (a) is a schematic diagram explaining the case where precleaning is not performed, (b) is the case where precleaning is performed. It is an electron microscope image which shows the effect of the silicon grain density control by the presence or absence of supply of the dopant gas in Example 2 of this invention, and the difference in supply timing. It is a figure which shows the supply timing of the silicon-type gas in Example 2 of this invention, and dopant gas. It is an image figure of the reaction form when not flowing (FIG. 9 (a)) when the dopant gas is flowed before the process of forming silicon grains and / or during the process (FIG. 9B). It is an electron microscope image which shows the effect of the silicon grain density control by the difference in the temperature in a process chamber, and a process pressure in the 3rd Example of this invention. It is a figure which shows the supply timing of silicon-type gas in Example 3 of this invention, dopant gas, and inert gas, and a process pressure. It is an image figure of the reaction form when the process which forms a silicon grain is performed at a low pressure (FIG. 12A) and when it is performed at a high pressure (FIG. 12B). It is an image figure of the reaction form when performing the process which forms a silicon grain at high temperature (FIG. 13 (a)), and when performing at low temperature (FIG.13 (b)). It is an image figure of the reaction form when the process which forms a silicon grain is performed by gas with a small flow rate (FIG. 14A) and when it is performed with a large flow rate (FIG. 14B). It is sectional drawing which shows a part of flash memory containing the floating gate comprised by the silicon quantum dot. It is sectional drawing which shows a part of DRAM containing the gate electrode comprised with the polysilicon film and metal film of a fine grain size.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Substrate processing apparatus 112 Wafer transfer machine 115 Elevator 202 Processing furnace 203 Reaction tube 207a Upper heater 207b Lower heater 208 Heat insulating material 231 Exhaust line 232a Gas introduction line 232b Gas introduction line 244 Gate valve 247a Temperature controller 248 Pressure controller 249 Main controller 250 Vacuum pump

Claims (3)

Carrying a substrate having an insulating film formed on the surface thereof into the processing chamber;
Introducing at least a silicon-based gas into the processing chamber, and performing a process of forming silicon grains on the insulating film formed on the surface of the substrate;
Unloading the substrate after processing from the processing chamber;
Have
In the step of performing the treatment, the flow rate of the dopant gas is changed between the silicon gas and the dopant gas in the treatment chamber set at a temperature and pressure such that the silicon gas is not thermally decomposed when the silicon gas is introduced alone. A method for manufacturing a semiconductor device, which is introduced so as to be equal to or higher than the flow rate of a silicon-based gas. Carrying a substrate having an insulating film formed on the surface thereof into the processing chamber;
Introducing at least a silicon-based gas into the processing chamber, and performing a process of forming silicon grains on the insulating film formed on the surface of the substrate;
And unloading the substrate after processing from the processing chamber,
In the step of performing the treatment, a silicon gas and a dopant gas are introduced into the treatment chamber set at a temperature and pressure such that the silicon gas is not thermally decomposed when the silicon gas is introduced alone, and a dopant gas is obtained. A method of manufacturing a semiconductor device in which the thermal decomposition of silicon-based gas occurs with the action of. A processing chamber for processing a substrate having an insulating film formed on the surface;
A silicon-based gas supply system for supplying a silicon-based gas into the processing chamber;
A dopant gas supply system for supplying a dopant gas into the processing chamber;
An exhaust system for exhausting the processing chamber;
A heater for heating the substrate in the processing chamber;
The temperature and pressure in the processing chamber are set to such a temperature and pressure that the silicon-based gas is not thermally decomposed when the silicon-based gas is introduced alone, so that the temperature and pressure are set in the processing chamber, A process of forming silicon grains on the insulating film formed on the surface of the substrate by introducing a silicon-based gas and a dopant gas so that the flow rate of the dopant gas is equal to or higher than the flow rate of the silicon-based gas. A controller for controlling the silicon-based gas supply system, the dopant gas supply system, the exhaust system, and the heater;
A substrate processing apparatus.